nazsox



components;

Patented Dec. 18, 1951 OFFICE NONCAKIN G COMPOSITIONS OF MATTER George Otis Funderburk, Upper Penns Neck, N. L,

assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Application October 5, 1949,

Serial No. 119,768

7 Claims. (Cl. 252-135) This invention relates to solid compositions of matter having increased physical stabilityagainst moisture. More particularly, this invention deals with the problem of hygroscopic solids which normally have a tendency to become softened when allowed to rest in contact with moisture, and which tend to agglomerate or become pasty if exposed to atmospheric humidity in finely divided form. In a special aspect, this invention is concerned with the preparation of commercial, solid detergents in stable, easily pourable, grain, pellet or powder form.

Soap and synthetic detergents have long been prepared for household use in a comminuted solid form, for instance, flakes, pellets or powders. Many of the syntheticdetergents, however, are hygroscopic or contain deliquescent consequently, stand in contact with a humid atmosphere, they often become caked together into relatively large agglomerates or may even become pasty. In both instances, their ready pourability is lost, and with it goes its practical advantages such as ease of transfer of the comminuted solid and its capacity of being measured out accurately, for household use, with a cup or spoon. When such detergents are manufactured in the form of bars or cakes, they still have the objectionable property of becoming softened and slimy in the soap dish. These defects have often constituted a great handicap in merchandizing synthetic detergents.

As examples of synthetic detergents to which this invention relates may be mentioned the alkane-sulfonate type, for instance the products prepared according to U. S. Patents Nos. 2,174,110 and 2,239,974; the alkaryl sulfonate type, for instance dode'cyl-benzene-sodium sulfonate (U. S. P. 1,992,160 and 2,232,118) and related products; the sulfo-alkyl-acylamide type, for instance the compound bat their hygroscopicity by admixing therewith inert water-insoluble powders such as tale. The disadvantage of such substances-in a detergent when allowed to is however obvious, inasmuch as the inert material does not readily wash out of the fiber when a textile fabric has been laundered with such an agent. The result is a fabric containing a loosely held powder in its fiber, which continuously rubs off in handling. Furthermore, any adjuvant to a detergent must stand certain additional tests; for instance, it should not tend to impart an objectionable color or odor to the final product and it should not diminish substantially the cleansing power of the principal constituent.

It is accordingly an object of this invention to provide a process for imparting to hygroscopic solids improved physical stability toward moisture. Another object of this invention is to provide means for discouraging the caking tendency of hygroscopic solids in comminuted form when exposed to the atmosphere. A special object of this invention is to provide synthetic detergents of improved physical properties. Other and further important objects of this invention will appear as the description proceeds.

Now according to my invention, the above objects are efdciently and economically achieved by incorporating into the hygroscopic solid one or more of the reaction products obtained by reacting a water-soluble aluminum salt with boric acid or a water-soluble :borate.

Such reaction products are, most likely, aluminum borates of the general formula :tAlzOa 113203 wherein a: and y are integers. Compounds of the above general formula wherein x=1 and :1, and wherein :c=3 and 11:1, have been recorded in the literature and have been referred to 27 times the molal quantity of aluminum salt (calculated as A1203) employed for the reaction.

The agents found suitable for this invention difier further from the basic aluminum :borates of the literature in their mode of preparation and their physical characteristics. Thus,

the agents with whichrthis invention deals are.v

produced by reaction in aqueous medium, and are of a soft character, colloidally dispersible in water, whereas the basic aluminum borates of the literature are produced by fusing the reactants together and are of a glassy, water-insoluble nature.

Where decrease of hygroscopic tendency of a solid is the only objective, any of the aforementioned aluminum polyborates are suitable, and they may be prepared for instance by reacting 1 part of aluminum sulfate with from 1 to 8 parts of anhydrous borax For use in detergents, however, it is preferable to select those rection products which contain from about to 9 boron atoms for each aluminum atom. This corresponds to reacting 1 part by weight of aluminum sulfate'w'ith from'about 1.5 to about 2.5 parts by weight of anhydrous borax.

It will be obvious, of course, that in all the reactions above mentioned, other water-soluble salts of aluminum and other water-soluble borates may be employed in the corresponding equivalent proportions. Aluminumchloride, aluminum nitrate, aluminum triacetate, ammonium alum and potassium alum may be mentioned as examples of such other Water-soluble aluminum salts; boric acid and sodium metaborate may be used in..1ieu of borax. Where anhydrous borax is mentioned, normal borax (NazBrOmlOHzO) or any intermediate hydration product may, of course, be employed, provided suitable adjustment in the weight selected is made.

Production of the above reaction products is best achieved in aqueous solution. For instance, separately prepared aqueous solutions of the two principal reactants, say aluminum sulfate and borax, may be mixed together; or one of said reagents may be added in 'powdered'form to a solution of the other. Sufiicient water should be employed to insure good contact and circulation of the reactants. Concentrated aqueous masses containing as high as 25% total dissolved and suspended material'may be employed, but better results are obtained with more dilute masses. The temperature of reaction may be kept at any point between room temperature and the boiling point, but the temperature range of 65 to 70 C. is recommended as most suitable. action product is in asemi-colloidal, gelatinous, highly dispersed condition, and does not settle out appreciably upon standin for several days.

The reaction products may be recovered in solid form by evaporating the above aqueous reaction mass to dryness in any convenient manner, for instance by spray dryin or drum drying.

The resulting dry solid is ground, if need be, to a fine powder, and may be admixed with the hygroscopic solid in any convenient manner, for instance by milling, or by dissolving the two jointly in water and evaporating to dryness. Many of the detergents above mentioned are normally prepared first in the form of an aqueous solution or suspension which is then evaporated in a spray drier or on a drum; it is, therefore, often convenient to mix the detergent and the protectin aluminum polyborate while each is' still in its aqueousreaction mass, and then evaporate the combined aqueous mass in a single operation.

The quantity of aluminum polyborate to be added may vary from 0.4 to 3.5 parts by weight for each part of detergent in the composition. If desired, other customary .adjuvantsmay be When prepared in this fashion, the represent, for instance common fillers or builders such as sodium sulfate, sodium carbonate, alkali-metal silicate (such as sodium meta-silicate, sodium sequisilicate), the alkali-metal polyphosphates such as sodium pyrophosphate, water-soluble cellulose derivatives (such as sodium carboxy-methyl-cellulose and sodium hydroxyethyl cellulose), and the like.

In certain cases, it is desirable to react the aforementioned aluminum polyborates with one or more of the abovementioned adjuvants separately, prior to incorporating either of them into the synthetic detergents. These variations of my general invention are described more fully and claimed in my copending application of even date herewith, Serial No. 119,769.

g It is interesting to observe that the aforementioned stabilizing effect against caking in humid atmosphere is by no means the only advantage imparted by said aluminum polyborates to synthetic detergents. I find that other very .valuable advantages are obtained incidentally, among which may be mentioned a perceptible whitening efiect on the dried composition, giving the product added sales appear. Also, aqueous .solutions of detergents containing my novel adjuvants have a soapy feel and appearance, which are generally lacking in most synthetic detergents. My adjuvants also have the quality of buffers, impartin to said aqueous detergent solutions a steady pH of about 9.0, at 0.6% total solids concentration; this is-true even when the composition contains alkaline builders which would normally cause the pl-I to be above 10.0.

Without limiting my invention, the following examples are given to illustrate my preferred mode of operation. Parts mentioned are by weight.

PART I. PREPARATION OF THE PROTECT- ING AGENT EXAMPLE 1 Nineteen parts of borax (corresponding to 10 parts of anhydrous borax) were dissolved in 250 parts of water at a temperature of 6570 C. Nine and one-half parts of crystalline aluminum sulfate (Al(SO4)a.18H2O, corresponding to approximately 5 parts of anhydrous aluminum sulfate) were added'gradually with agitation. Mixing was continued for 3 minutes, whereupon the milky reaction mass was dried on a drum dryer to an anhydrous powder. The white powder was found to be readily dispersible in water, to yield a gelatinous, milky suspension, apparently identical in all respects with the milky reaction product from which it was obtained. Both possess the property of stabilizing hygroscopic powders against agglomeration inhumid atmosphere, as more fully discussed in Part II hereinbelow.

EXAMPLE 2 Nine and one-half parts of crystalline aluminum sulfate (18H2O), were dissolved in 250 parts of water at 6570 C., and 19 parts of powdered borax were added gradually with stirring. From here on the procedure was the same as. in Example l, and the results were essentially the same.

EXAMPLE v3 A quantity of aluminum sulfate corresponding to 5 parts of A12(SO4) 3 and a quantity of borax corresponding to 10 parts of 'NazBiov were reacted together in 250 parts of water as in the aforegoing examples. .An amount corresponding to lpart of sodium carboxymethyl cellulose .(pow-.

amaze tier) was dropped into the resulting solutionwith;

A quantity of aluminum sulfate" corresponding to 5 parts of A12(SO4)3 and a quantity of borax corresponding to 10 parts of NazBiOv were'reacted together in 500 parts of water as in the foregoing examples. Into the resulting solution, 18 parts of tetrasodium pyrophosphate- (beads) were entered with stirring until dissolved, The

mass was then stirred for fifteen minutes, at which time it was observedto be aclear S Q1l ltion. It was then dried to a powder upon a drum dryer. 7

EXAMPLE 5 g i ll quantity of aluminum, sulfatecorresponding to 5.parts of A12(SO4)3 and-a quantity of borax,

. EXAMPLE 6 A quantity of aluminum sulfate corresponding to 5 parts of Al2(SO4)3 and a quantity of borax corresponding to 10 parts of NazBiOz were re-- I acted together in 350, parts of water as in the foregoing examples. Into' the resulting reaction mass was dropped a quantity of granular sodium sesquisilicate (NaaI-I Si04.5Hz), corresponding to 6 parts of NasH S104, with stirring until dissolved. The reaction mass was then dried to a powder on a drum dryer.

EXAMPLE 7 A quantity of aluminum sulfate, corresponding to parts of A12(SO4)5 and a quantity of borax corresponding to IOparts of NazBrOv were reacted together in '350 parts of water as in the foregoing examples. Six parts (anhydrous basis of sodium sesquisilicate were dropped into the resulting solutions with stirring'until dissolved. Into the reaction mass was then dropped inone part-of sodium carboxymethyl cellulose, with stirring until dissolved. The reactionmass was dried "to a powder on a drum dryer. EXAMPLES ,A quantity of aluminumsulfatefcorresponding' to 5 parts of A12(SO4)3 and a quantity of borax corresponding to parts of NazBloa were reacted together in 200 parts of water as in the foregoing examples. 1T0 the resulting solution was added 6 parts of sodium sesquisilicate (anhydrous) with stirringuntil dissolved. To this reaction mass 18 parts of tetrasodium pyrophos pliate were added. After stirring for minutes, solution of all ingredients was complete and the solution was considerably less milky than'initially. The reaction mass was dried to a powder on a drum dryer. The resulting dry product'jupon the addition of water, formed only slightly turbid;

at concentrations of or essentially clear solutions 1.0% solids or less.

EXAMPLE An aqueous reaction mass was prepared in a manner identical to that of Example 8, and then one part of sodium carboxymethyl cellulose was ssl. ad l y with fiir i sactil. diss ved..

d The resulting final aqueous mass was dried to a powder on a drum dryer with essentially the same results as in Example 8. a

EXAMPLE 10 It was found that after the aluminum polyborate was formed, as in the aforegoing examples, sodium carboxymethyl cellulose could be added before or after any or all of any subsequent reactants or ingredients with substantially the same results.

f EXAMPLE 11 The procedure was the same as in Example 2 except that the quantity of water used was only 45' parts. As the borax was added, it dissolved and reacted more and more slowly. However, with suflicient agitation, solution and reaction appeared complete, though the mass was quite viscous. When a small amount was diluted with water, it appeared identical to the product made in Example 2.

. EXAMPLE 12 The procedures were the same as in previous examples except that the quantities employed were varied as indicated below, and the various products prepared were not evaporated. Instead, they were used directly to protect detergent compositions against moisture as indicated in Part II herein below.

The variations embraced in this series of ex periments were as follows: Using one part of Al2(SO4)3, the Na2B4O7 was varied from 1 to 8 parts. The quantity of water was varied from 15 to times the total weight of these two reactants.

PART II. PREPARATION OF DETERGENTS A. Dry mixing EXAMPLE 13 Fifteen parts of a drum-dried detergent powder containing 5.25 parts of an alkane-sodium-sulfonate (average chain length, 16 C-atoms, pre-. pared according to U. S. P. 2,239,974) 1.5 parts" of anhydrous borax (Na2B4O7) and 8.25 parts of sodium sulfate (Na2SO4) and 15 parts of the drum-dried product obtained in Example 1 were mixed together intimately. The product was allowed to stand for several days in a humid atmosphere whose relative humidity was artificially maintained at 81% (at F.). A control sample was prepared by mixing 15 parts of the same. detergent powder with 15 parts of sodium sulfate (anhydrous), without any of the agent prepared in Example 1. The control sample became pasty after 8 days, whereas the protecteds'ample remained physically unchanged (dry; and easily pourable) even after 14 days.

' EXAMPLE 14 cally unchanged (dry and easily pourable) even after 14 days.

. EXAMPLE 15 --In a similar manner, the products obtained in Examples ,4, 5, 6, 7, 8 and 9 were incorporated with a dry detergent powder as in Example '14.- 11mmexposure to 81%. relative humidity, 'allofthese samples showed tremendously improved resistance to becoming pasty and non-pourable compared to the control samples. 1

B. Wet mixing XAMP re A quantity of crystalline aluminum sulfate corresponding to 5 parts of -A12(SO4)3, was dissolved in 1000 parts of water at 65-,70.-C. A quantity of powdered borax corresponding to parts of Na2B4O7 was added slowly to this solution, with agitation until the reaction was complete. To this reaction mass was added and dissolved a quantity of commercial powdered sodium carboxymethyl cellulose containing 37.5% active ingredient, 25% .NaCl and 37.5% water and corresponding to '2 parts of pure sodium .carboxymethyl cellulose. To the resulting reaction: mass were further added and dissolved, 5.4 parts of crystalline anhydrous :NazSOa. A quantity of a liquid crude concentrate of .an .alkane sodium sulfonate (average chain length 15470; prepared according to U. S. Patentj2,239,974) corresponding to 20 parts of active ingredient and containing further, 7 parts combined of NaCl and Nazsol plus an undetermined amount of unreacted alkane, was added to the reaction mass. Mixing was continued to a homogeneous condition and the reaction mass was dried to a powder on a drum dryer. Drying removed .essentially all of the water and the .unreacted allgane.

, A control sample was prepared by dissolving 69 parts of anhydrous NazSOr in 1000 parts --of water, and adding thereto an amount of sodium carboxymethyl cellulose powder corresponding to 2 parts of the active ingredient, mixing until dissolved. To this solution was added and dis solved a quantity of the aforementioned alkane sodium sulionate crude concentrate corresponding to 20 parts of the active ingredient and 7 parts of mixed inorganic salts. The Whole mass. was dried to a powder on a drum dryer.

The protected sample and the control sample were tested by exposure to 81% relative humidity. The control sample became pasty in two days while the protected sample remained essentially unchanged (dry and easily pourable) even after fourteen days. 7

The detergent composition of this example also exhibited superior whiteness compared .to the control sample and when dissolved in water possessed a soapy feel and appearance.

The detergency powers .of both samples were determined by the method described in the American Dyestufi Reporter, December 13, 1945, pages 556-561 and were found to be essentially equal.

EXAMPLE 17 In a similar manner, using 225 parts of water to start, a, composition was prepared essentially identical to the composition of Example 16, ex-' cept, that the sodium carboxymethylcellulose was omitted and the amount of Naasoi added was increased by a corresponding amount. The controlsample prepared in Example 16 was used. Upon testing the-compositional: this example for resistance to atmospheric humidity (81% R. v-I-I.), essentially .the same results as in Example 16 were obtained. .Its detergency power, tested as .previously described, was undiminished.

EXAMPLE 18 Ina similar manner, and using the same ingredients, a composition was prepared, using 400 parts of water to start, containing'20 parts of alkane sodium sulfonate, 5 parts of NazBiO'r/ 5 parts of A12(SO4')-3, 2'parts of sodium carboxy methyl cellulose, and 68 parts of inorganic salts.

Compared to the control sample prepared in Example 16, essentially the same results were obtained with respect to physical stability to atmospheric'humidity, and the 101-101 a 1% aqueous solution was 4. 5.

EXAMPLE 19 Ina similar manner, and using the same ingredients,;a composition was prepared, using 1000 parts of water to start, containing 20 parts of of alkane sodium-sulfonate,-40 parts of NazBtO-r, 5 parts of A12(SO4)3,,2 parts of sodium carboxymethyl cellulose, and 33'parts of mixed inorganic salts. Again compared to the control sample from Example 16, essentially the same results were obtained with .respectto physical stability to atmospheric humidity. Tested as described, its detergency power was found to be essentially undiminished.

EXAMPLE 20 Using thesame procedure and ingredients, and starting with 120.0'parts of water, a composition was prepared which when dried contained .20 parts of :alkane sodium sulfonate, 46 parts of NazBiO'z, 23 parts of A12(SO 4)3, .2 partsof sodium carboxymethyl cellulose, and 12 parts of inorganic salts. The composition of this example was compared to the control sample of Example 16 with respect to physical stability to atmospheric moisture and detergency power with essentially-the'sameresults as were obtained with previous examples.

ents, -,a composition was prepared, starting with 500 parts of water, whichcontained when dried.

35 parts of alkane sodium sulfonate, 10 parts of Na2B4O'1, 5 parts of .Al2(SO4)3, and 50 parts of mixed inorganic salts.

A control sample was prepared by dissolving a quantity of borax corresponding to 10 parts of N942B4O7 in 500 parts of water, dissolving therein 44 parts of NazSO4 and adding to the solution a quantity of crude concentrate of alkane sodium sulfonate corresponding to 35 parts of the active ingredient and 11 parts of mixed inorganic salts. a powder on a drum dryer.

Comparing the composition of' this example with the control sample, the protected sample was again 'found to possess definitely superior physical stability to atmospheric humidity while its 'detergeney powers remain undiminished.

" EXAMPLE 22 was dropped into this solution with agitationuntilthe reaction was complete. To this re The final solution was dried to fate corresponding to parts of A12(SO4)3.

. product.

action mass was then added 58 parts of crystalline Na2so4 (anhydrous) with mixing until dissolved.

A quantity of' the same alkane sodium suldonate crude concentrate used in Example 16, corresponding to 20 parts of the active ingredient and '7 parts of mixed inorganic salts was then added and dissolved in the mix. Finally, the whole mass was dried to a powder on a drum dryer.

Compared to the control sampleused in Example 16 the composition of this example was found to have substantially the same improved physical stability when exposed, to atmospheric humidity as the compositions of previous examples.

EXAMPLE 23 Four separate compositions were prepared in an identical manner, following the procedure of Example 22, except that in each case a different water-soluble aluminum salt was used as follows:

(A) Potassium alum, K2SO4A12(SO4=)3-24H2O 23.6 parts.

(B) Aluminum acetate, A1(C2H3O2)3 (24% solution)-,40 parts of the solution.

(C) Aluminum chloride, (anhydrous), A1C13 6.7 parts.

(D) Aluminum nitrate,

parts.

It was found that in compositions (C) and (D) the aluminum polyborate formed was acid.

Before proceeding further with these two com- In200 parts of water, at 65-'70 C. was dissolved a quantity of crystalline aluminum sulfate corresponding to 5 parts of A12(SO4)3. A quantity of powdered boric acid corresponding to parts of HsBOs was added slowly to this solution with agitation until dissolved and reacted. The pH of the subsequent reaction mass was adjusted to between 7 and 8 with 10% NaOI-I. From here on the procedure was the same as in Example 22 and the results obtained were essentially the same.

EXAMPLE 2% In 200 parts of water, at 65-70 0., was dissolved a quantity of crystalline aluminum sul- A quantity of powdered sodium metaborate corresponding to10.6 parts of NaBOz was added slowly to this solution, with agitation, until dissolved and reacted. From here on the procedure was the same as in Example 22 and the results obtained were essentially the same.

C. Polyphosphates and silicates Water-soluble polyphosphates and silicates, such as sodium pyrophosphate and sodium sesquisilicate, are well known adjuvants to detergents, acting as builders therefor and contribut ing in general to the cleansing qualities of the In my present invention I have found them, moreover, to exert a hydrotropic eifect on 10 the aluminum polyborate, clarifying cloudy suspensions of the latter within certain'concentration limits. To get the maximum benefit from this angle, it is desirable to enter the pyrophosphates and silicates to the aqueous mass in which the aluminum polyborate has been prepared, prior to entering the detergent compound. If sodium carboxymethyl cellulose and inorganic salts are also employed, these may be dissolved in the aqueous reaction mass either prior to, simultaneously with or subsequent to the addition of the pyrophosphate. The procedure in such cases is illustrated by the following examples.

EXAMPLE 26 6.5 parts of A12 SO4 3 were dissolved in 800 parts of water, at -70 C., and a reaction mass was formed by adding thereto, slowly, 13.5 parts of Na2B40'1- A quantity of commercial powdered sodium carboxymethyl cellulose corresponding to 2 parts of active ingredient and also containing 2 parts of NaCl was next added. to the reaction mass and dissolved, followed successively by 22 parts of NazSO4 .and 27 parts of tetrasodium pyrophosphate. Mixing was continued for fifteen minutes, whereupon the solution became clear. Thereupon a quantity of the same alkane sodium sulfonate crude concentrate used in Example 16, corresponding to 20-parts of active ingredient and '7 parts of mixed inorganic salts was added and dissolved by mixing. The mass was dried to a powder on a drum dryer.

Compared to the control sample used in Example 16, for physical stability to atmospheric humidity, the controlsample became pasty in two days while the protectedsample remained essentially unchanged for twelve days. I

The protected sample was whiter in color than the control sample and its water solutions possessed a soapy feel and appearance. A 0.6% product concentration of the composition of this example in water had a pH of 8.7. A similar composition not containing the protecting agent would be expected'to have a pH of 10.0-10.5. The detergency power of the composition of this example, based upon-aknowledge of the building effects derived from the use of tetrasodium pyrophosphate, waseven better than expected.

EXAMPLE 27 EXAMPLE 28 Using 230 parts of water, a reaction mass was prepared containing 6.5 parts of Alz(SO4)3 and 13.5 parts-of NazBrOw. An amount of granular sodium sesquisilicate corresponding to 5.5 parts of Na3HSiO4 was added to this reaction mass and dissolved, followed by dropping in and dissolving an amount of powdered sodium carboxymethyl cellulose corresponding to 2 parts of active ingredient and 2 parts of NaCl. I An amount of crystalline Nazsoi equivalent to 9 parts and an amount of tetrasodium pyrophosphate equivalent to 27 parts were added together to the reaction mass, which was further agitated for fifteen min- .utes, whereupon a definite-clearing of the reactionmass was noticed. An amount of thesame alkane sodium sulfonate used in Example 16 corresponding to 20 parts of active ingredient and 7 parts of mixed inorganicsalts was added to the reaction mass and agitated until dissolved. The mass was dried to'a powder'on. a drum dryer.

The same control sample used in Example 16 was used in this example. Upon exposure to 81% relative humidity, the control sample became pasty in two days while the protected sample remained unchanged, even after fourteen days. Its

detergenoy power was definitely superior to the control sample.

EXAMPLE 29 A sampleidentical to the composition of Example 28 was prepared, except that sodium meta silicate (Na2SiO3)- was substituted for sodium ses'quisilicate. The results obtained were essentially the same;

EXAMPLE 30' I A composition was prepared in an identical manner to the composition in Example 28 except that it contained 20' parts of alkane sodium sulfonate', parts ofA1z(SO4)3, part'sofNazB4O7, 515 parts 0fNa3HSiO4, 1 part of sodium carboxymethyl cellulose, 18 parts of tetrasodium pyrophosphate, 8.5 parts of mixed inorganic salts, and 32 parts of added Na'zSOr.

A similar composition was prepared which containedhowever 32parts of added NaCl in place of Na2SO4.

Comparing both. these compositions with the composition of Example 28, for detergency. powers and'physical stability to. atmospheric humidity, all three compositions were foundto give essentially the same results.

EXAMPLE 31' 'Acomposition was prepared which: was identi-- cal to the? composition of Example 30 exceptthat only 150 parts of water were used in preparing the aqueous mix. This composition: was found to be. essentially identical to' the composition of ExampleBO in allrespects.

EXAMPLE 32 A composition was prepared which wasessentially identical to the composition of 'Example 28 except that it contained 36'parts of tetrasodium pyrophosphate and no sodium sulfate wa'sadded. It was compared to the compositions of Examples 28, 29, 30 and'31 and found to be essentially equal to them in all respects.

D. M isc'ellcmeousi detergents In theforegoing examples li'have adhered persistently to detergents of the. alkane-sulfona'te type, for the sake of bringing out clearly the effectsof the variations from one example to the next. My invention is, however, by no means limited to the particular. class, and improves the physical qualities of any hygroscopic detergent. But the" degree of improvement may vary from case to case, depending on how severely hygroscopic a given class of'detergentsis to begin with. This is illustrated by the following examples.

EXAMPLE 33 A reaction mass containing 500 parts of water at 6570 C., 1'7- parts ofNazBiOv, and'8 parts of A12.(SO4)3 was prepared. Into this reaction mass was dropped, with stirringuntil dissolved, at quantity of a dry detergent powder (containing 40% activeingredient and 60% Na2SO4) corresponding to 30 parts of an alkyl aryl: sodium sulfonate .preparedaccording to-U. S. P. 2,314,929, and 45 parts of Na2SO4; The reactionmass was dried to a powder on a drum dryer.

A control sample was prepared in; a similar manner by dissolving 25- parts of NazSO4 in 500 parts of water and adding. thereto the aforementioned detergent. powder in an amount equivalent to 30 parts of alkyl aryl sodium sulfonate and 45 parts of Na2SO4.

Mixing was continued until solution was complete and the mass was then dried to apowderon a drum dryer.

Upon exposure to 811% relative humidity for several days, the control sample became pasty. in six days-while the protected sample remainedvirtually unchanged for at least fourteen days. Detergency power, measured as previously mentioned, was essentially the same for bothsamples.

The detergent'composition of this example also exhibited superior whiteness compared to the control sample, and when dissolved in water; possessed a soapy feel and appearance, which the control sample did not.

EXAMPLE 34 A similar composition was prepared, usinga sulfo-alkyl-acylamide of U. S. Patent 1,932,180 of the type assthe detergent active ingredient.

A reaction mass was prepared as in Example 33 using 1000 parts of water, at 65-70 C.', 15 parts of Na2B407, and '7 .5 parts of A12(SO4)3. To this reaction mass wasadded, with stirring: until dissolved, a quantity of a dry detergent powder corresponding to 23 partsof a sulfo-alkyl-acylamide of. the formula (U. S. P. 1,932,180), which also containedv the equivalent of 54.5 parts of miscellaneous. salts, chiefly sodium chloride. The final reaction mass was dried to a powder on a drum dryer.

A control sample was prepared by dissolving'25 parts of. crystalline NaCl in 750 parts of water, at. 65-70 C. and further dissolving in this solution, a quantity of the aforementioned detergent powder corresponding. to 20 parts of the active ingredient and 55 parts of salts. The final solution was dried to a powder on a drum dryer.

This type of active ingredient is very hygroscopic. Testing by exposure to 81% relative humidity, as before, the control sample became pasty in only two days while the protected sample remained unchanged for eight days. Test showed. that the detergency power of the protected and control sample were essentially equal.

EXAMPLE 35 A water solution, containing 9% NaCl and 25% of C-cetyl betaine represented by the formula Ci5H33-CH-N(CH 3)3 oc-o prepared according to U. S. Patent 2,129,264, was used in this example.

Using 500 parts of water, a reaction mass-containing 15 parts of A12(SO4)3 and 30 parts of NazB4O7 was prepared. To this reaction mass were added and dissolved 21 parts of NazSO4. Then, a quantity of the above mentioned liquid betaine product was added, corresponding to 25 parts of active ingredient and 9 parts of NaCl.

.humidity and tested for detergency power.

After thorough mixing, the reaction mass was dried to a powder on a drum dryer.

A control sample was prepared by dissolving 66 parts of crystalline NazSO4 in 500 parts of water and adding thereto an amount of the liquid betaine product corresponding to 25 parts of active ingredient and 9 parts of salts. The resulting solution was dried on a drum dryer. The result was a product in the form of a putty like mass entirely unfit for use as a dry pourable product, while the protected sample was a dry, easily pourable powder. Upon exposure to 81% relative humidity atmosphere, the protected sample remained unchanged for two days while the control sample became very wet and pasty in less than one day. The protected samples were tested for detergency power and found to be essentially undiminished.

It will benoted here that long chain betaine compounds are extremely hygroscopic and cannot EXAMPLE 36 Alcohol sulfates made from alcohols manufactured from olefins by the x0 process, as described in F. I. A. T., Final Report #1000, are hygroscopic and are benefitted by the incorporation of aluminum polyboratesaccording tothis invention.

In this example, the alcohol sodium sulfate used was a mixture of various chain lengths (exact proportions unknown), which can be represented by the formula:

R-CH -CH-GHz-O-SOgNa wherein R=alkyl (8 to 18C) R =H or alkyl (1 to SC) and R+R =12 to 18C.

Using 200 parts of water, a reaction mass was prepared containing 10 parts of A12(SO4)3 and 20 parts of NazBrOv. In this mass was dissolved 40 parts of Na2SO4 and to the resulting mixture was added an amount of a water solution of the aforementioned alcohol sodium sulfates corresponding to 30 parts. After mixing to a homogeneous solu tion, the reaction mass was dried to a powder on a drum dryer.

A control sample was prepared in a similar manner, omitting the aluminum polyborate protecting agent and increasing the NazSO4 to 70 parts to compensate.

Both samples were exposed to 81% relative At 81% R. H., the control sample became pasty in less than one day, while the protected sample remained unchanged for 5 days. power was found to be essentially undiminished.

EXAMPLE 37 Using 1000 parts of water a reaction mass was prepared as in Example 26 containing 5'part's of A12(SO4)3, parts of Na2B4O7, parts of tetrasodium pyrophosphate, and 33 parts of NazSOt. To the clear solution of these ingredients was added and dissolved a quantity of a semi-liquid crude concentrate of an alkyl-aryl sodium sulfonate corresponding to 30% active ingredient and 7% Na2SO4. (This material was prepared by sulfonation and subsequent hydrolysis with NaOI-I of an alkane product prepared according to U. S. P. 2,477,382.) The final solution was dried to a powder on a drum dryer.

Its detergency 1'4 A control sample containing 15 parts of tetrasodium pyrophosphate, 55 parts of NazSO4, and 30 parts of active ingredient was prepared in a similar manner.

Both samples were tested by exposure to 81% relatively humidity atmosphere. The control sample became pasty and non-pourable in 9 days while the protected sample remained'unchanged even after 14 days. Its detergency power was essentially undiminished.

EXAMPLE 38 Using 230 parts of water, a reaction mass was prepared containing 10 parts of A12(SO4)3, parts of Na2B4O1, 5.5 parts of NaaHSiO i, 10 parts tetrasodium pyrophosphate and 29.5 parts of mass was dried to a powder on a drum dryer.

1 A control sample was prepared in a similar manner which contained parts of active ingradient, 10 parts of tetrasodium pyrophosphate,

and'65 parts of Na2SO4.

When tested at 81% relative humidity atmosphere, the control sample became pasty in 4 days while the protected sample remained in good condition for 11 days. Thedetergency power of the composition of this example was undiminished compared to the control sample.

EXAMPLE 39 Using 230 parts of water, a reaction mass was prepared by dissolving therein 5 parts of A12(SO4)3 and further adding slowly, 10 parts of NfiiiBOl followed by an amount of sodium sesquisilicate corresponding to 5.5 parts of NasHSiO4 which was mixed until dissolved. Into the re action masswas dropped with stirring until dissolved, 1 part of sodium carboxymethyl cellulose. 18 parts of tetrasodium pyrophosphate and 22 parts of Na2so4 were added together to the. reaction mass and stirred until dissolved. The mass was agitated for fifteen minutes whereupon a noticeable clearing of the milky mix was observed. To the mass was then added a quantity of the crude aqueous concentrate used in Example 37 corresponding to parts of alkyl aryl sodium sulfonate and '7 parts of NazSO4. The

mass was agitated until homogeneous and was then dried to a powder in a drum dryer.

The control sample used in Example 37 was also used in this example.

Upon testing at 81% relative humidity, the control sample became pasty in 9 days while the protected sample remained unchanged, even after 14 days. Its detergency power was essentially undiminished.

g 4 EXAMPLE 40 -A composition was prepared, using 1200 parts 'of water at -'70 C. in which was dissolved mentioned solution and mixed until homogene- 15 ous;- The-mass was thendried to a powder on a drum dryer;

A control sample was prepared by dissolving-80 part of Na2SO4 in 1200 parts of water-and adding, thereto, an amount of the C-cetyl betaine corresponding to 15 parts of active ingredient and also containing. 5 parts of NaCl. The mass was then dried on a drum dryer; The resulting prod.- uct was tacky and damp. like wet sawdust,. entirely unfit for use as an easily pourable product.

Both samples were tested by exposure to 81% relative humidity. The control sample became very in less than one day while the protected sample retained its original easilypour- 'abl'e characteristics for 3 days.

Both samples" were tested for detergency powers, as previously described. The protected sample was found to be very definitely superior to the control sample.

EXAMPLE 41. g

A compositionv was prepared based. upon sulfo-alkyl acylamide detergent (U. 8;. R. 1,932,183). 12 parts of AlMSQi); were dissolved in 3G0 parts of water at 6540 (3.. followed by 24. parts of NazBiOv, and reacted as in previous examples. A quantity of sodium sesqui silicate corresponding to 12; parts of NaaHSiOi was dissolved in this reaction mass, followed by the addition of 42 parts of tetrasodium pyrophosphate. Mixing was continued for 15: minutes, whereupon a slight clearing of the reaction mass was noticeable. A quantity of. an aqueous gel of the aforementioned sulfo-alkyl acylamide detergent corresponding to 10 parts of active ingredient was then added to the reaction mass, which. was mixed until homogeneous and dried to a powder on a drum dryer.

A control sample was prepared by dissolving 99 parts of NaCl in 500 parts of water'and adding thereto, an amount of the sulfo-alkyl a'cylamide gel. corresponding to 10 parts of active ingredient, mixing until homogeneous, and drying to a powder on a drum dryer.

Both samples were tested by exposure to 81% relative humidity. The control sample became pasty in 2 days, while the protected sample remained easily pourable for 8 days.

The detergency powers of both samples were tested as described. The protected sample was found to be definitely superior to the control sample.

E. Product in bar form.

'mass' This is illustrated by the following example;

EXAMPLE 42 In a manner similar to previous examples, a compositioncontaining 35 parts of the alkane sodium sulionate of Example 16-, 10 parts of Nae-a407, 5 parts of Alz(SO4)a, and 50 parts of inorganic salts (38 parts of NazSO added): was prepared and drum dried to a powder.

A control sample containing 35 parts of ab- 'kanesodium: sulfonate,- 1.0 parts of. NazBiOv,

and 55 parts of inorganic salts (43 parts of NaQSO'i. added) was prepared and dried to a powder on a drum. dryer.

Using a moldv andra hydraulic press, 20 gms. of: both samples. were compressed under 10 tons/sq. in. pressure to cakes approximately 2 inches in diameter and inch thick. Each low surface film. of soft, pasty material, while the control sample was. soft throughout: and could: be. easily crushed to a pasty mass. After allowing-both cakes to air-dry for one hour under room conditions: (temperature 809-455 F.-'' relative-humidity 70-75%), they were both examined again- The. composition, of this example:was' essentially dry and? firm. while the control sample wassoit, wet, and pasty.

The above procedure was repeated with respect to the products obtained in. Examples 26 and 30' hereinab ove,. with equally. good results.

It will be clear from the above. examples that my invention may be, varied considerably without departing from the essence of this. inventlon. Thus, the ratio of aluminum polyborate to the weight of the detergent (active ingredient) may be. varied within wide limits. A ratio of 0.20 oreven less may suflice under circumstances to give a perceptible improvement, while the upper limit of this ratio is governed entirely by the economics of the situation. If the article to be manufactured justifies the higher. cost, the entire filler content of. the detergent (normally, sodium sulfate) may be replaced by aluminum polyborates. (Inv certain .commercialscouring powders, the. quantity of filler is often as high as. 97% by weight or, the entire composition.)

In addition; the article may contain other customary builders and fillers, for instance; sodium sulfate, sodium chloride or borax, in quantity'of from 10 to 94% of the total weight of the composition; soluble silicates in quantity of from 1 to 20% of total weight; talc, volcanic ash, ground silica or other comminuted solids, from 0 to 97% by weight; sodium carboxymethyl cellulose or sodium hydroxy-ethyl' cellulose, in quantity from 0.5 t 40%. by weight; and other customary ad'- juvants for commercial detergents.

The aforegoing pointsare illustrated further by the following examples:

EXAMPLE 43C O'MPOSITION CONTAINING N a SOi AS. FILLER One part of M20804); was dissolved in 2,000 parts- .01 water at 65 to 70 C. Two parts of NEHB407WEI'9 then, added slowly, with agitation to form an. aqueous dispersion of aluminum polyborate.- 282 parts. of Na2SO4.. were then dis solvedin the reaction mass. 15 parts (on active ingredient basis) of alkane sodium sulfonate were 17 corresponding to 15 parts of active ingredient. The mass was dried to a powder on a drum dryer. The two powders obtained above were exposed to 81% relative humidity atmosphere as previously described. The composition containing aluminum polyborate possessed greatly improved physical stability to atmospheric moisture, and its detergency power was essentially undiminished.

EXAMPLE 44-COMPOSITION CONTAINING AN EXCESS OF THE NOVEL COMPLEX As FILLER Following the technique of Example 43, a reaction mass of aluminum polyborate was prepared which contained 2,000 parts of water, 60 parts of A12(SO4)a and 120 parts of NaZBQO'L To this reaction mass was added a quantity of the same crude alkane sodium sulfonate used in Example 43, corresponding to 20 parts of active ingredient. The mass was agitated until homogeneous and dried to a powder on a drum dryer.

The dry powder was found to have good physical stability to atmospheric humidity. Its detergent power was essentially undiminished.

In Examples 43 and 44 above, as well as in Examples 16 to 32 inclusive, Wherever alkane sodium sulfonate is named, the same compound as specified in Example 16 was employed. The invention, however, is not limited thereto, and any commercial alkane sulfonate detergent, having from 12 to 18-0 atoms, may be employed in lieu thereof.

Furthermore, although all the specific examples of this application are concerned particularly with detergents, my invention is applicable for improving the stability against moisture of other solids, for instance fertilizers, sawdust, common hygroscopic salts and the like.

In the foregoing examples and in the claims hereinbelow, where drum-drying f a given composition is indicated, drying to a final moisture content of below 1% by weight is to be understood.

In the discussion hereinabove I have employed the expression synthetic detergents in a limited sense; that is, excluding ordinary soap, which is an alkali-metal salt of a long-chain fatty acid. Inasmuch, however, as in a more general sense soaps are also synthetic products, I employ in the claims hereinbelow the expression non-soap wherever I wish to signify that a particular claim is to be construed as subgeneric to the aforementioned synthetic detergents without including ordinary soaps.

I claim as my invention:

1. A composition of matter comprising a hygroscopic solid and the water-dispersible reaction product obtained by reacting in aqueous medium a quantity of water-soluble aluminum salt equivalent to 1 part by weight of aluminum sulfate with a quantity of a compound selected from the group consisting of boric acid and water-soluble borates equivalent to from 1 to 8 parts byweight of anhydrous borax, the quantity of said reaction product in the composition being equal to at least 0.4 times the weight of said hygroscopic solid, and the entire composition being characterized by increased physical stability toward moisture compared to the hereinabove mentioned hygroscopic solid by itself.

2. A composition of matter comprising a hygroscopic solid and an aluminum polyborate in quantity of 0.4 to 3.5 parts by weight for each unit weight of said hydroscopic solid, said aluminum polyborate being the product obtained by reacting in aqueous medium a quantity of a watersoluble aluminum salt equivalent to 1 part by weight of aluminum sulfate with a quan ity of a compound selected from the group consisting of boric acid and water-soluble borates equivalent to from 1 to 8 parts by Weight of anhydrous borax, and the entire composition being characterized by increased physical stability toward moisture compared to the hereinabove mentioned hygroscopic solid by itself.

3. A composition of matter as in claim 2, the hygroscopic solid being a non-soap synthetic detergent.

4. A composition of matter adapted for use as a cleansing agent, coniiprising a water-soluble, solid, hygroscopic, non-soap, synthetic detergent in comminuted form, and an aluminum polyborate in quantity of 0.4 to 3.5 parts by weight for each part of active detergent, said aluminum polyborate being the waterdispersible reaction product obtained, by reacting in aqueous medium a water-soluble aluminum salt in quantity equivalent to 1 part by weight of aluminum sulfate with a water-soluble borate in quantity equivalent to from 1.5 to 2.5 parts by weight of anhydrous borax, and the entire composition being characterized by a reduced tendency to cake upon exposure to humid atmosphere compared to the tendency of the aforementioned hygroscopic detergent solid by itself.

5. A composition of matter as in claim 4, comprising further an auxiliary agent selected from the group consisting of alkali-metal polyphosphates and alkali-metal silicates.

6. A composition of matter as in claim 4, comprising further an agent selected from the group consisting of detergent builders and inert fillers.

'7. A composition of matter adapted for use as an adjuvant to hygroscopic, non-soap, synthetic detergents, said composition comprising on the one hand the water-dispersible reaction product of 1 part by weight of aluminum sulfate with from 1.5 to 2.5 parts by weight of anhydrous borax, and on the other hand at least one detergent-auxiliary selected from the group consisting of alkali-metal polyphosphates and alkalimetal silicates.

GEORGE OTIS FUNDERBURK.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Switzerland Sept. 1, 1945 

1. A COMPOSITION OF MATTER COMPRISING A HYGROSCOPIC SOLID AND THE WATER-DISPERSIBLE REACTION PRODUCT OBTAINED BY REACTING IN AQUEOUS MEDIUM A QUANTITY OF A WATER-SOLUBLE ALUMINUM SALT EQUIVALENT TO 1 PART BY WEIGHT OF ALUMINUM SULFATE WITH A QUANTITY OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF BORIC ACID AND WATER-SOLUBLE BORATES EQUIVALENT TO FORM 1 TO 8 PARTS BY WEIGHT OF ANHYDROUS BORAX, THE QUANTITY OF SAID REACTION PRODUCT IN THE COMPOSITION BEING EQUAL TO AT LEAST 0.4 TIMES THE WEIGHT OF SAID HYGROSCOPIC SOLID, AND THE ENTIRE COMPOSITION BEING CHARACTERIZED BY INCREASED PHYSICAL STAPARTS BY WEIGHT OF ANHYDROUS BORAX, THE QUANTITY ABOVE MENTIONED HYGROSCOPIC SOLID BY ITSELF.
 4. A COMPOSITION OF MATTER ADAPTE DOR USE AS A CLEANSING AGENT, COMPRISING A WATER-SOLUBLE SOLID, HYGROSCOPIC, NON-SOAP, SYNTHETIC DETERGENT IN COMMINUTED FORM, AND AN ALUMINUM POLYBORATE IN QUANTITY OF 0.4 TO 3.5 PARTS BY WEIGHT FOR EACH PART OF ACTIVE DETERGENT, SAID ALUMINUM POLYBORATE BEING THE WATER-DISPERSIBLE REACTION PRODUCT OBTAINED, BY REACTING IN AQUEOUS MEDIUM A WATER-SOLUBLE ALUMINUM SALT IN QUANTITY EQUIVALENT TO 1 PART BY WEIGHT OF ALUMINUM SULFATE WITH A WATER-SOLUBLE BORATE IN QUANTITY EQUILVALENT TO FROM 1.5 TO 2.5 PARTS BY WEIGHT OF ANHYDROUS BORAX, AND THE ENTIRE COMPOSITION BEING CHARACTERIZED BY A REDUCED TENDENCY TO CAKE UPON EXPOSURE TO HUMID ATMOSPHERE COMPARED TO THE TENDENCY OF THE AFOREMENTIONED HYGROSCOPIC DETERGENT SOLID BY ITSELF. 